Zeolite synthesis in fluoride media: structure direction toward ITW by small methylimidazolium cations

Pure silica ITW zeolite can be synthesized using 1,2,3-trimethylimidazolium and 1,3-dimethylimidazolium cations and fluoride anions as structure-directing agents (SDAs). Similarly to the previously reported 1,3,4-trimethylimidazolium, the dimethyl cation can also produce the zeolite TON, but this higher framework density phase finally transforms in situ into ITW. The structures of the as-made and calcined phases prepared with the new cations show a unit cell doubling along z, and the refined structures are reported. Periodic Density Functional Theory calculations provide the energies of the six SDA-ITW and SDA-TON zeolites, and their relative stabilities fully agree with the experimental observations. Structure-direction in this system is discussed from experimental and theoretical results that give strong support to the idea that strained silica frameworks are made possible in fluoride media by decreasing the covalent character of the Si-O bond. This decreased covalency is enhanced with the 1,2,3-trimethyl isomer, which is shown to be the strongest SDA for ITW and, at the same time, is the more hydrophilic of the three SDAs tested. Our observations with the three SDAs agree with the so-called Villaescusa's rule, i.e., the low framework density phase is favored at higher concentrations, but at the same time question the supersaturation hypothesis that has been proposed to explain this rule, since here the low-density phase is the most stable one.     

Processing of high resolution magic angle spinning spectra of breast cancer cells by the filter diagonalization method

Proton nuclear magnetic resonance ((1)H NMR) spectroscopy for detection of biochemical changes in biological samples is a successful technique. However, the achieved NMR resolution is not sufficiently high when the analysis is performed with intact cells. To improve spectral resolution, high resolution magic angle spinning (HR-MAS) is used and the broad signals are separated by a T(2) filter based on the CPMG pulse sequence. Additionally, HR-MAS experiments with a T(2) filter are preceded by a water suppression procedure. The goal of this work is to demonstrate that the experimental procedures of water suppression and T(2) or diffusing filters are unnecessary steps when the filter diagonalization method (FDM) is used to process the time domain HR-MAS signals. Manipulation of the FDM results, represented as a tabular list of peak positions, widths, amplitudes and phases, allows the removal of water signals without the disturbing overlapping or nearby signals. Additionally, the FDM can also be used for phase correction and noise suppression, and to discriminate between sharp and broad lines. Results demonstrate the applicability of the FDM post-acquisition processing to obtain high quality HR-MAS spectra of heterogeneous biological materials.     

The discriminants associated to isotropy representations of symmetric spaces

We consider a generalized discriminant associated to a symmetric space which generalizes the discriminant of real symmetric matrices, and note that it can be written as a sum of squares of real polynomials. A method to estimate the minimum number of squares required to represent the discrimininant is developed and applied in examples.     

Anderson localization in nonlocal nonlinear media

We theoretically and numerically investigate the effect of focusing and defocusing nonlinearities on Anderson localization in highly nonlocal media. A perturbative approach is developed to solve the nonlocal nonlinear Schr?dinger equation in the presence of a random potential, showing that nonlocality stabilizes Anderson states.     

Introducing axial chirality into mesoionic 4,4'-bis(1,2,3-triazole) dicarbenes

Mesoionic 4,4'-bis(1,2,3-triazole-5,5'-diylidene) Rh(I) complexes having a C2 chiral 4,4'-axis were accessed from 3-alkyltriazolium salts in virtually complete de. Their structure and configurational integrity were assessed by NMR spectroscopy, X-ray crystallography, and chiral HPLC. Computational analysis of the MICs involved in the reaction suggested the formation of a highly stable and unprecedented cation-carbene intermediate species, which could be evidenced experimentally by cyclic voltammetry analysis.     

Cordifolide A, a sulfur-containing clerodane diterpene glycoside from Tinospora cordifolia

Cordifolide A (1), a novel unprecedented sulfur-containing clerodane diterpene glycoside, together with other two new diterpene glycosides, cordifolides B (2) and C (3), and four known analogues, was isolated from a methanol-soluble extract of the stems of Tinospora cordifolia. The structures of the new compounds were determined on the basis of spectroscopic data interpretation, with that of cordifolide A (1) confirmed by a single-crystal X-ray crystallographic analysis. All isolates were evaluated for their in vitro immunomodulatory activity using mouse bone marrow-derived dentritic cells (BMDCs).     

Essential oil composition and acaricidal activity of Schinus terebinthifolius from Atlantic Forest of Pernambuco, Brazil against Tetranychus urticae

The compositions of the essential oils from unripe (UFr) and ripe (RFr) fruits of Schinus terebinthifolius were analyzed by GC and GC/MS. The major compound identified in both oils was limonene (UFr = 44.1 +/- 1.3%; RFr = 31.8 +/- 1.2%), followed by alpha-phellandrene (15.7 +/- 0.4%) in the UFr oil and thujene (21.7 +/- 0.9%) in the RFr oil. Repellent and toxicity activities of the two oils were also evaluated, and the results compared with eugenol. The UFr oil was more active in the fumigation tests (LC50 = 1.46 microL/L of air), whereas the RFr oil was more active in the sealed dishes (SD) than open dishes (OD) contact assay (LC50 = 3.04 microL/cm2) and not significantly different from eugenol. Both oils exhibited significant repellent activity comparable with that of eugenol. The results suggest that the repellent activity of these oils in association with its toxicity could be a great advantage for the integrated management of T. urticae.     

Exponential decay and resonances in a driven system

We study the resonance phenomena for time periodic perturbations of a Hamiltonian $H$ on the Hilbert space $L^2\left({\mathbb{R}}^d\right)$. Here, resonances are characterized in terms of time behavior of the survival probability. Our approach uses the Floquet–Howland formalism combined with the results of L. Cattaneo, J.M. Graf and W. Hunziker on resonances for time independent perturbations.     

Silicene: compelling experimental evidence for graphenelike two-dimensional silicon

Because of its unique physical properties, graphene, a 2D honeycomb arrangement of carbon atoms, has attracted tremendous attention. Silicene, the graphene equivalent for silicon, could follow this trend, opening new perspectives for applications, especially due to its compatibility with Si-based electronics. Silicene has been theoretically predicted as a buckled honeycomb arrangement of Si atoms and having an electronic dispersion resembling that of relativistic Dirac fermions. Here we provide compelling evidence, from both structural and electronic properties, for the synthesis of epitaxial silicene sheets on a silver (111) substrate, through the combination of scanning tunneling microscopy and angular-resolved photoemission spectroscopy in conjunction with calculations based on density functional theory.     

A matter-dominated cosmological model with variable G and Λ and its confrontation with observational data

In the framework of renormalization-group improved cosmologies, we analyze both theoretically and observationally the exact and general solution of the matter-dominated cosmological equations, by using the expression of the cosmological term as a function of the Newton parameter already determined by the integration method employed in a previous paper. A rough comparison between such a model and the concordance ΛCDM model from the point of view of the magnitude-redshift relationship has been already considered, without showing any appreciable differences. Here we test our model by using astrophysical data (the Union2 type Ia supernovae (SNIa) dataset, the Hubble diagram constructed from some gamma ray bursts luminosity distance indicator), to constrain its parameters. We also apply a cosmographic approach to our cosmological model. In order to estimate the cosmographic parameters we fit a large dataset, including not only the Hubble diagram, as traced by SNIa and gamma ray bursts, but also the H(z) measurements from passively evolving galaxies, baryon acoustic oscillations and the distance priors from the cosmic microwave background radiation anisotropy spectrum. We show that this matter-dominated cosmological model with variable Newton parameter and variable cosmological term is indeed compatible with the observations above. The cosmographic approach adopted confirms such conclusions. Last, it seems possible to include radiation into the model, since numerical integration of the equations derived by the presence of both radiation and matter shows that, after inflation, the total density parameter is initially dominated by the radiation contribution and later by the matter one.